新型含吡啶环氟化二胺及其共聚聚酰亚胺的合成与性能

以3-羟基苯乙酮和苯甲醛为原料,通过改进的Chichibabin反应制备了4-苯基-2,6-双（3-羟基苯基）吡啶（m-PHPP）,再将其与2-氯-5-硝基三氟甲苯反应,合成了硝基化合物4-苯基-2,6-双[3-（4-硝基-2-三氟甲基苯氧基）苯基]吡啶（m,p-6FPNPP）,最后用Pd/C和水合肼将m,p-6FPN...     

Click Chemistry of Selenium Dihalides: Novel Bicyclic Organoselenium Compounds Based on Selenenylation/Bis-Functionalization Reactions and Evaluation of Glutathione Peroxidase-like Activity

A number of highly efficient methods for the preparation of novel derivatives of 9-selenabicyclo[3.3.1]nonane in high yields based on selenium dibromide and cis,cis-1,5-cyclooctadiene are reported. The one-pot syntheses of 2,6-diorganyloxy-9-selenabicyclo[3.3.1]nonanes using various O-nucleophiles including alkanols, phenols, benzyl, allyl, and propargyl alcohols were developed. New 2,6-bis(1,2,3-triazol-1-yl)-9-selenabicyclo[3.3.1]nonanes were obtained by the copper-catalyzed 1,3-dipolar cycloaddition of 2,6-diazido-9-selenabicyclo[3.3.1]nonane with unsubstituted gaseous acetylene and propargyl alcohol. The synthesis of 2,6-bis(vinylsulfanyl)-9-selenabicyclo[3.3.1]nonane, based on the generation of corresponding dithiolate anion from bis[amino(iminio)methylsulfanyl]-9-selenabicyclo[3.3.1]nonane dibromide, followed by the nucleophilic addition of the dithiolate anion to unsubstituted acetylene, was developed. The glutathione peroxidase-like activity of the obtained water-soluble products was estimated and compounds with high activity were found. Overall, 2,6-Diazido-9-selenabicyclo[3.3.1]nonane exhibits the highest activity among the obtained compounds.     

Push-pull-Butadiene. XII. Darstellung von Hetrocyclen aus 2,6-Bis[bis(alkylthio)methylen]cyclohexylidenmalononitrilen

Preperations of Heterocycles by using of 2,6-Bis[bis(alkylthio)methylene]cyclohexylidenemalononitriles . 2,6-Bis[bis(alkylthio)methylene]cyclohexylidenemalonitriles 1 react with alkanethioles to give 1,3-bis(alkylthio)-5-[bis(alkylthio)methylene]-5,6, #7,8-tetrahydro-isoquinoline-4-carbonitriles 2 . Treatment of 1 with hydrogen bromide yields 4,6,7,9-tetrakis(alkylthio)-2,3-dihydro-5,8-diaza-phenalenes 3 . On the other hand, 1 can be converted with bromine to 6,9-bis(alkylthio)-4,7-dibromo-2,3-dihydro-5,8-diaza-phenalenes 5 . However, the reaction of 1 and N-bromosuccinimide afforded 2,6-bis[bis(alkylthio)methylene]-3-bromo-cyclohexylidenemalononitriles 8 .     

Novel magnesium and zinc porphyrazines containing galactose moieties: Synthesis via click reaction and characterization

In this study, galactose conjugated new magnesium and zinc porphyrazines were synthesized by the cyclotetramerization reaction of 2,3-bis[1-(2,2,7,7-tetramethyltetra-hydro-bis[1,3]dioxolo[4,5-b;4′,5′-d]pyran-5,methyl)-1H-[1,2,3]triazol-4-yl methylsulfanyl]-but 2-enedinitrile. This substituted dicyano compound was prepared via two different routes. One started from cis-1,2-dicyano-1,2-ethylenedithiolate disodium, [1-(2, 2, 7,7-tetramethyltetrahydrobis[1,3]dioxolo[4,5-b;4′,5′-d]pyran-5-yl-methyl)-1H-[1,2,3]triazo-l-4-yl]methanol and ended in a multi-step reaction sequence via Click procedures. The other reaction was between 5-azidomethyl-2,2,7,7-tetramethyltetrahydro-bis[1,3]dioxolo[4,5-b;4′,5′-d]pyran and (2Z)-2,3-bis(prop-2-yl-1-yl-thio)but-2-enedinitrile. A very soluble galactose linked magnesium porphyrazine derivative in common polar solvents and water was achieved by the deprotected isopropylidene groups in TFA and water media. It is first time, zinc porphyrazine complex has been achieved at one-step reaction by using Zn(BuO)₂ as template agent. The new compounds have been characterized by a combination of elemental analysis, ¹H, ¹³C NMR, IR, UV–vis and MS spectral data.     

Diels-Alder Reactions of in situ generated N-benzoylindolo-2,3-quinodimethane with carbodienophiles

The indolo-2,3-quinodimethane ( 5 ), generated from 2,3-bis(bromomethyl)indole ( 4 ), was trapped with unsymmetrical carbodienophiles or N, N′-p-phenylenedimaleimide to furnish the 1,2,3,4-tetrahydrocarbazoles ( 6 – 9 ). [4 + 2]-Cycloaddition of 5 with tetracyanoethylene gave rise to the tetracyanocarbazole ( 10 ) and a subsequent product 11a or 11b . The Diels-Alder reaction of 5 with divinyl sulfone was regiospecific within the detection limits of HPLC analysis. Similarly, the reaction of 5 with N, N′-p-phenylenedimaleimide yielded solely the stereoisomer 9 .     

Reactions with β-ketodianilides. I. New synthesis of Pyrido[3,4-c]pyridine Derivatives

Acetonedicarboxylic acid dianiline reacted with malononitrile, ethyl cyanoacetate or benzoylacetonitrile to give (6-amino-5-cyano-1,2-dihydro-2-oxo-1-phenylpyrid-4-yl)-acetanilide ( 3 ), (3-cyano-2,6-dioxo-1-phenyl-1,2,5,6-tetrahydropyrid-4-yl)acetanilide ( 8 ) or (3-cyano-1,6-dihydro-1,2-diphenyl-6-oxopyrid-4-yl)acetanilide ( 9 ). Compounds 3 and 8 could be cyclised into 8-amino-1,6-diphenyl-1,2,4,5,6,7-hexahydro-7-iminopyrido[3,4-c]pyridine-2,5-dione ( 4 ) and 7-amino-1,2,3,5,6,8-hexahydro-1,6-diphenylpyrido[3,4-c]pyridine-2,5,8-trione ( 10 ) respectively by heating their solutions in dimethylformamide in the presence of triethylamine. Each of 3 and 4 coupled with arenediazonium chlorides to give the corresponding arylhydrazone derivatives ( 5a–d ) and ( 6a–c ), respectively. Condensation of 4 with p-nitrosodimethylaniline yielded 8-amino-4- (p-dimethylaminophenylimino)-1,6-diphenyl-1,2,4,5,6,7-hexahydro-7-iminopyrido[3,4-c]pyridine2,5-dione ( 7 ).     

Regioselectivity of Oxysulfenylations of Cycloocta-1,5-diene

The regioselectivity of transannular O-heterocyclization of cycloocta-1,5-diene ( 1 ) with phenylsulfenyl chloride and methanol or water, respectively, is determined by the oxy-component which acts as nucleophilic partner in the electrophilic three component reaction. The thermodynamically more stable endo, endo-2,6-bis(phenylsulfenyl)-9-oxabicyclo[3.3.1]nonane ( 2 ) is formed almost exclusively in methanol while the isomeric 9-oxabicyclo[4.2.1]nonane ( 3 ) is favored under kinetic control in the presence of water. The oxidation of 2 or 3 yields the bissulfones 4 and 5 , respectively.     

新型含吡啶环二胺及其可溶透明性氟化聚酰亚胺的合成与表征

以4-三氟甲基苯甲醛和3-(4-硝基苯氧基)苯乙酮(m,p-NPAP)为原料,通过改进的Chichibabin反应制备了硝基化合物4-(4-三氟甲基苯基)-2,6-双[3-(4-硝基苯氧基)苯基]吡啶(m,p-3FPNPP),再用Pd/C和水合肼将m,p-3FPNPP进行还原,成功制备了一种新型含吡啶环的芳香二胺4-(4-三氟甲基苯基)-2,6-双[3-(4-胺基苯氧基)苯基]吡啶(m,p-3FPAPP)。以m,p-3FPAPP作为二胺,3,3′,4,4′-二苯醚四羧酸二酐(ODPA)作为二酐,N,N-二甲基甲酰胺(DMF)为溶剂,通过常规的两步法,经热或者化学亚胺化形成聚酰亚胺,制得了一种新型的含吡啶环聚酰亚胺。所得聚酰胺酸和聚酰亚胺的粘度分别为0.78 dL/g和0.65 dL/g。化学亚胺化所得的聚酰亚胺速溶于常见有机溶剂如DMF、N,N-二甲基乙酰胺(DMAc)、N-甲基-2-吡咯烷酮(NMP)、四氢呋喃(THF)等。制得了柔韧的聚酰亚胺膜,膜有很好的热稳定性,玻璃化转变温度(Tg)为234.4℃,氮气氛中10%失重温度为575.3℃,膜有很好的光学透明性,截止波长为369 nm,同时,膜还有较好的力学性能,拉伸强度为96.4 MPa,拉伸模量为1.63 GPa,断裂伸长率为9.2%,膜的吸水率为0.68%。     

Synthesis and Properties of Novel Polycyanurates Derived from 2-(N-piperidino)-4,6-bis (naphthoxy-2-carbonyl chloride)-s-triazine

Various polyamides containing s-triazine rings in the main chain were synthesized by high temperature polycondensation of 2-(N-piperidino)-4,6-bis(naphthoxy-2-carbonyl chloride)-s-triazine [PNCCT] with various aromatic diamines such as 4,4′-diaminodiphenyl [DADP], 4,4′-diaminodiphenylamide [DADPA], 4,4′-diaminodiphenylsulphone [DADPS], 4,4′-diaminodiphenylsulphonamide [DADPSA], 4,4′-diaminodiphenyl methane [DADPM], 2,4-diamino toluene [DAT] and p-phenylene diamine [PPDA]. All the polyamides were characterized by viscosity measurements, IR spectra, NMR spectra, and thermogravimetric analysis.     

Novel Copolyamides Based on s-Triazine Derivatives

Ten copolyamides have been synthesized by polycondensation of 2-(N-methylpiperazine)-4,6-bis(2-naphthoxy-6-carbonyl chloride)-s-triazine [MPNCCT] and different mixtures of diamines such as; 4,4′-diamino diphenylamide [DADPA] + 4,4′-diamino diphenyl sulphone [DADPS]; 4,4′-diamino diphenylamide [DADPA] + 4,4′-diamino diphenylmethane [DADPM]; 4,4′-diaminodiphenylamide [DADPA] + p-phenylene diamine [PPDA]; 4,4′-diaminodiphenylamide [DADPA] + ethylene diamine [EDA]; 4,4′-diaminodiphenylamide [DADPA] + 2,4-diamino toluene [DAT]; 2,4-diamino toluene [DAT] + 4,4′-diaminodiphenyl sulphone [DADPS]; 2,4-diamino toluene [DAT] + 4,4′-diaminodiphenyl sulphonamide [DADPSA]; 2,4-diamino toluene [DAT] + 4,4′-diaminodiphenyl methane [DADPM]; 2,4-diamino toluene [DAT] + o-phenylene diamine [OPDA] and p-phenylene diamine [PPDA] + 4,4′-diaminodiphenyl sulphonamide [DADPSA]. All the copolyamides have been characterized by IR spectra, NMR spectra, solubility, density, viscosity measurements and thermogravimetric analysis [TGA]. The obtained products, have high thermal stability along with good solubility in organic solvents.     

Synthesis of Thiazolo(4,5-b)-quinoxalines and related compounds

The reaction of 2,3,7-trichloroquinoxaline ( 1 ) or 2,3-dichloro-7-bromoquinoxaline ( 2 ) with thiourea in DMSO gave 6,6′-dichloro- or 6,6′-dibromodiquinoxalino[2,3-b:2′:3′-e]1,4-dithiien ( 3 or 4 ). However, 1 or 2 reacts with thiourea in ethanol to give ( 3 or 4 ) beside 7-chloro- or 7-bromo-2-imino-2,3-dihydrothiazolo[4,5-b] quinoxaline ( 5 or 6 ) respectively. Interaction of 1 or 2 with acetone thiosemicarbazone gave 7-chloro- or 7-bromo-3-amino-2-imino-2,3-dihydro-thiazolo[4,5-b] quinoxaline hydrochloride ( 13 or 14 ) respectively. Cyclization of 7-chloro- or 7-bromo-3-amino-2-imino-2,3-dihydrothiazolo[4,5-b]quinoxaline ( 15 or 16 ) on treatment with aromatic acid chlorides or isothiocyanates succeeded to give 19—21 or 28 and 29 .     

Orthoamide. L. Beiträge zur Chemie von Propiolaldehydaminalen – Synthesen und Umsetzungen zu Push–Pull-substituierten Buta-1,3-dienen,Cyclobutanen sowie vinylogen Amidiniumsalzen und 1,2,3-Triazolen

Orthoamides. L. Contribution to the Chemistry of Propiolaldehydaminales – Synthesis and Transformations to Push–Pull-substituted Buta-1,3-dienes, Cyclobutanes, Vinylogous Amidinium Salts and 1,2,3-Triazoles Tert-butylaminalester 5 reacts with terminal alkynes to give aminals of substituted propiolaldehydes 3c, d . The aminal 3a is accessible from N,N,N′,N′-tetramethylformamidinium chloride (7b) and sodium acetylide. The aminals 3b,c can also be prepared from bis(dimethylamino)acetonitrile 8 and terminal alkynes in the presence of sodium hydride. The nitrile 8 is also useful for the preparation of the bis-aminal of acetylenedialdehyde 6 . The aminal 3e can be transaminated by heating with secondary amines to give the aminals 3f–i . The aminals 3a–i react with strong CH₂-acidic compounds (pK_a between 9 and 14) to give the 1-dialkylamino-1,3-butadienes 10 . The isomeric 1-dialkylamino-butadienes 18 can be obtained from the condensation of the CH-acidic cinnamic acid derivatives 19 with dimethylformamidedimethylacetal. CH and NH-acidic compounds as cyanacetamide react with the aminals 3c,e exclusively with the acidic methylene group to produce the enamines 10h,t . The acylformamidine 21 can be obtained from 10t and tert-butylaminalester 5 . The pyridone 22 is accessible from the condensation product 10h by thermal cyclization. The pyrido[2,3-d]pyrimidine 26 is formed in the reaction of the 6-amino-uracile 23 with the aminal 3a . In an unexpected reaction the 1,2-bis(cyano-dialkylaminomethylene)-cyclobutanes 28a–d result from the action of trimethylsilylcyanide on the aminals 3e–h . The corresponding reaction with trimethylsilylisothiocyanate affords the vinylogous amidinium thiocyanates 34a, b . In the reaction of trimethylsilylazide and the aminals 3 are produced the 4-(dialkylaminomethylene)-4H-1,2,3-triazoles 38 .     

Synthesis,Thermal Stability and Impact Stability of Novel Tetranitro‐Dipyridotetraazapentalene Derivatives

The synthetic details for the construction of three new dipyridotetraazapentalene derivatives, 5H‐pyrido[3″,4″:4′,5′] [1,2,3]triazolo‐ [1′,2′:1,2][1,2,3]triazolo[5,4‐b]pyridin‐6‐ium inner salt ( 8 ), 5H‐pyrido[3″,2″:4′,5′] [1,2,3]triazolo[1′,2′:1,2] [1,2,3]triazolo[5,4‐b]‐pyridin‐6‐ium inner salt ( 15 ) and 5H‐pyrido[2″,3″:4′,5′] [1,2,3]‐triazolo[1′,2′:1,2][1,2,3]triazolo[4,5‐b]pyridin‐6‐ium inner salt ( 16 ) are presented. Nitration of ( 8 ) and ( 15 ) afforded the novel tetranitrodipyridotetraazapentalene derivatives, 2,4,8,10‐tetranitro‐5H‐pyrido[3″,4″:4′,5′][1,2,3]triazolo[1′,2′:1,2][1,2,3]‐triazolo[5,4‐b]‐pyridin‐6‐ium inner salt ( 3 ) and 2,4,8,10‐tetranitro‐5H‐pyrido[3″,2″:4′,5′][1,2,3]triazolo[1′,2′:1,2][1,2,3]‐triazolo[5,4‐b]‐pyridin‐6‐ium inner salt ( 4 ) in good yields. Both isomers, ( 3 ) and ( 4 ), exhibited high thermal stability (differential scanning calorimetric analysis and thermal gravimetric analysis) and were insensitive to impact (hammer/anvil test).     

Regio- and stereoselectivity of 1-(Pyridazin-3-yl)-3-oxidopyridinium Betaines towards 2π- and 4π-conjugated olefins

1-(6-Phenyl) and 1-(6-(4-tolyl)-3-oxidopyridinium betaines ( 1a , b ) react as 1,3-dipoles with conjugated olefines, namely 4-vinylpyridine, ethyl cinnamate and styrene as 2π-1,3-dipolarophiles to give 2,6-cycloadducts [6-substituted-8-azabicyclo[3,2,1]oct-3-en-2-ones ( 3a , b , 4a , b and 5b )] and with butadiene and furan as 4π-dipolarophiles to give 2,4-cycloadducts [7-substituted-7-azabicyclo[4,3,1]deca-3,8-diene-10-one] and 3-6-phenylpyridazin-3-yl)-3-aza-10-oxatricyclo-[5,2,1,1^2,6]undeca-4,8-diene-11-one ( 9a ). Structural and configurational assignments were based on H.n.m.r. spectral analysis.     

Intramolekulare 1,3-dipolare Cycloadditionen von Arylaziden mit Alkinylsubstituenten

Intramolecular 1,3-Dipolar Cycloadditions of Aryl Azides with Alkynyl Substituents Reaction of substituted 4-chlorobut-2-ynes 1 with 2-acetaminophenol and 2-aminothiophenol, respectively, leads to the corresponding ethers and thioethers 3 that can be converted into the alkynyl substituted aryl azides 4 by diazotation and reaction with sodium azide. Intramolecular 1,3-dipolar cycloaddition yields 4H-[1,2,3]triazolo [5,1-c] [1,4] benzoxazines and benzothiazines 5 . In the same way 1,4-bis(2-acetaminophenoxy)but-2-yne 6 reacts to a 3-(2-azidophenoxy-methyl)-triazolobenzoxazine 9 . Its thermal decomposition gives the azomethine 11 .     

Interpenetrating polymer networks derived from epoxide-amine adducts in either polymer network

A new type of interpenetrating polymer network was synthesized via photoinitiated free-radical polymerization of α,ω-methacryloyl terminated macromonomers prepared from epoxide-amine-adducts, followed by thermal addition polymerization of bisphenol-A diglycidyl ether and 4,4′-diaminodiphenylsulfone or 3(4),8(9)-bis(aminomethyl)tricyclo[5.2.1.0.^2,6]decane. The interpenetrating polymer networks are optically transparent and show only one glass transition temperature ranging from -10 to 130°C, as a function of the macromonomer/addition polymer mixing ratio. The presence of a single phase was confirmed by scanning electron microscopy (SEM).     

Synthesis of pyrazolo[4′,3′:5,6]pyrazino[2,3-c]pyrazoles and pyrazolo[4′,3′:5,6]pyrazino[2,3-d]pyrimidines and their application to polyester fibres

4-Nitroso-1-phenyl-3-methyl-5-aminopyrazole ( 1 ) was condensed with ethylcyanoacetate ( 2 ), malononitrile ( 4a ) and 2-cyanomethylbenzimidazole ( 4b ) to yield 6-hydroxy-5-cyano, 6-amino-5-cyano and 6-amino-5-(benzimidazol-2-yl)-3-methylpyrazolo [3,4-b]pyrazines 3, 5a and 5b , respectively. 5-Cyano-6-chloro derivative 6 obtained from 3 was converted to 3-aminopyrazolo[4′,3′:5,6]pyrazino[2,3-c]pyrazoles 8a and 8b by the treatment with hydrazin hydrate ( 7a ) and phenylhydrazine ( 7b ), respectively. Compound 5a was treated with formamide ( 9a ), urea ( 9b ) and thiourea ( 9c ) to give 4-aminopyrazolo[4′,3′:5,6]pyrazino[2′3′-d]pyrimidines 10a–10c. With refluxing acetic anhydride compounds 8a, 8b and 10a gave corresponding acetamido derivatives 8c, 8d and 10d. Compound 5a was treated with ethylorthoformate ( 11 ), acetic anhydride ( 12 ) or benzoylchloride ( 13 ) to give fused benzimidazopyrazolo[4′,3′:5,6]pyrazino[2′,3′-d]pyrimidines, viz., benzimidazol[1,2-c]pyrazolo[4,3-g]pteridines ( 14a–14c ). Some of the compounds 8, 10 and 14 were applied to polyester as disperse dyes and their fastness properties were studied.     

Reaction of ethyl N-(6-ethoxycarbonyl-2-methylthiothieno[2,3-d]-pyrimidin-5-yl) formimidate with alkyl- and arylhydrazines: Formation of modified thieno[2,3-d]pyrimidines and thieno[2,3-d:4,5-d]dipyrimidin-4-ones

The reaction of ethyl N-(6-ethoxycarbonyl-2-methyl-thiothieno[2,3-d]pyrimidin-5-yl)formimidate ( 1 ) with methyl-hydrazine, N,N′-dimethyl- and N,N′-diphenylhydrazines separately in refluxing ethanol resulted in hydrolysis of formimidate group to give ethyl 5-amino-2-methylthiothieno[2,3-d] pyrimidine-6-carboxylate ( 2 ). The reaction on 1 with methyl-hydrazine without solvent afforded ethyl 5-amino-2-(1-methyl-hydrazino)thieno[2,3-d]pyrimidine-6-carboxylate ( 3 ), which underwent hydrazone formation with p-nitrobenzaldehyde to give 4 . Treatment of 1 with N,N-dimethylhydrazine afforded a mixture of 3-dimethylamino-7-methylthiothieno[2,3-d:4,5-d']dipyrimidin-4(3H)-one ( 5 ) and 2 . Displacement of methylthio group in 5 with morpholine, piperidine and 4-methylpiperazine gave the corresponding 7-substituted derivatives 6a-c . The reaction of 1 with para-substituted phenylhydrazines resulted in the formation of 3-(p-substituted phenylamino)7-methylthiothieno[2,3-d:4,5-d']dipyrimidin-4 (3H)ones ( 7a-c ).     

Highly Regioselective DABCO‐Catalyzed Nucleophilic Aromatic Substitution (SNAr) Reaction of Methyl 2,6‐Dichloronicotinate with Phenols

Exclusive formation of 6‐aryloxy ethers 9 from an S_NAr reaction of methyl 2,6‐dichloronicotinate ( 2 ) with phenols 7 catalyzed by 1,4‐diazabicyclo[2.2.2]octane (DABCO) in the presence of stoichiometric triethylamine is described. The reaction proceeds via the regioselective formation of an unprecedented DABCO‐pyridine adduct 10a .     

Synthesis and Characterization of Polyamides Based on s-Triazine Moiety

Seven polyamides containing s-triazine rings in the main chain were synthesized by high temperature polycondensation of 2-(β-naphthylamino)-4,6-bis(naphthoxy-3-carbonyl chloride)-s-triazine [NANCCT] with various aromatic diamines such as 4,4′-diaminodiphenyl [DADP], 4,4′-diaminodiphenylamide [DADPA], 4,4′-diaminodiphenylsulphone [DADPS], 4,4′-diaminodiphenylsulphonamide [DADPSA], 4,4′-diaminodiphenyl methane [DADPM], 2,4-diamino toluene [DAT] and p-phenylene diamine [PPDA]. All the polyamides were characterized by solubility tests, density measurements, viscosity measurements, IR spectra, NMR spectra, and thermogravimetric analysis. The polyamides had inherent viscosities in the range 0.88–1.16 g/dL in N,N′-dimethyl formamide at room temperature (30°C). All the polyamides showed good thermal stability at high temperatures and most of them were soluble readily at room temperature in polar solvents.